Anionic slurry seal emulsifiers

ABSTRACT

An anionic emulsifier obtained from the reaction products of an alkyl phenol, polyamine, and formaldehyde or of an alkyl phenol, fatty acid/polyamine condensate, and formaldehyde followed by the reaction of such products with acrylic acid, and the uses of the emulsifier in anionic bituminous emulsions and paving slurry seal mixtures are disclosed.

BACKGROUND OF THE INVENTION

(1) Field of the Invention

This invention relates to slurry seal emulsions. More particularly, itrelates to novel emulsifiers for solventless and solvent containing,mixing grade, oil-in-water anionic bituminous emulsions, whichemulsifiers are derived from the reaction products of alkyl phenols,aldehydes and polyamines, post-reacted with acrylic acid.

(2) Description of related art

In paving operations, three main practices are employed to achievethorough mixing of bitumen and aggregate:

(1) mixing of free flowing heated asphalt (asphalt cement) withpre-dried aggregate;

(2) mixing pre-dried aggregate with asphalt diluted with a hydrocarbonsolvent (cutback asphalt, cutter stock) at ambient temperatures; and

(3) mixing aggregate with asphalt emulsions, e.g., oil-in-wateremulsions, obtained by vigorous agitation of asphalt and water in thepresence of an emulsifying agent.

Because of increasing cost in energy and hydrocarbon solvent and becauseof environmental concerns, the use of emulsified asphalt is increasing.

Conventionally, emulsion slurry seals are formulated from mineralaggregate which is a fine stone aggregate and/or mineral filler and amixing-grade, quick-setting or slow-setting emulsion containingbituminous residue (usually asphalt), and water to attain slurryconsistency. Usually, densely-graded aggregates, such as granitescreening, limestone screening, dolomite screening and blast furnaceslag, are combined with bituminous emulsions to produce slurry sealcompositions.

When a slurry seal is used in paving and road maintenance, the mixtureof emulsified bituminous material and fine-grained aggregate is held insuitable suspension until applied to the road surface. The slurry sealemulsion is of an oil-in-water type.

Depending on the emulsifier used to achieve an emulsion, anionic orcationic emulsions are obtained. In anionic emulsions, asphalt dropletsare negatively charged; in cationic emulsions, the asphalt droplets bearpositive charges.

In a bituminous emulsion formulated using anionic emulsifiers thebituminous material is deposited from the emulsion on calcareousaggregate due to the attraction of polar charges between the negativelycharged bituminous droplets and positively charged aggregate surfaces.

Anionic bituminous emulsions are taught by Wright and Mertens in U.S.Pat. No. 3,062,829 to be prepared by employing alkali emulsifier andpolyamide additives which are the condensation products of dilinoleicacid and polyalkylene polyamines. Lignin amines are taught as anionicemulsifiers in U.S. Pat. No. 3,123,569 to Borgfeldt. Also, Moorer, inU.S. Pat. No. 3,956,002, teaches an anionic emulsifier consisting of anoxygenated alkali lignin, an ethylene oxide adduct of alkylphenol, andup to 10% by weight of sodium borate; and, in U.S. Pat. No. 4,088,505,he teaches an anionic emulsifier consisting of an alkali metal salt ofan alkali lignin, an ethylene oxide adduct of alkylphenol and water. Inaddition, Montgomery and Pitchford teach the alkali metal salts ofcomplex polynuclear aromatic polycarboxylic acids as anionic asphaltemulsifiers in U.S. Pat. No. 3,344,082. Heinz, in U.S. Pat. No.3,006,860, similarly employs alkali metal soaps of higher fatty acids asthose found in tall oil.

Ferm, in U.S. Pat. No. 3,740,344, teaches the preparation ofquick-setting anionic slurry seal compositions by applying a combinationof anionic emulsifiers such as aryl alkyl sulfonates and condensationproducts of ethylene oxide with alkylated phenols, with fatty alcohols,with mono-esters of fatty acids with glycerol or sorbitol or long chainfatty acids. H. G. Schreuders, in U.S. Pat. No. 3,615,796, teaches theuse of petroleum sulfonates as quick-setting anionic slurry sealemulsifiers. A combination of sodium lignate or lignosulfonate andsaponified rosin or tall oil is described in U.S. Pat. No. 3,594,201 bySommer and Evans. Also, Conn, in U.S. Pat. No. 3,350,321, describes theuse of alkyl or alkoxy-alkyl phosphoric acids as emulsifiers forasphalts.

The use of tallow quaternary ammonium salts and tallow diquaternarydiammonium salts for making emulsions suitable for slurry seal insolventless applications is described in U.S. Pat. No. 3,764,359 toDybalski.

The uses of acidified reaction products of certain polycarboxylic acids,anhydrides, sulfonated fatty acids and epoxidized glycerides withcertain polyamines as emulsifiers yielding asphalt emulsions which canmixed with fine grained aggregate to give workable aggregate/emulsionmixes are disclosed in U.S. Pat. No. 4,447,269 to Schreuders et al.,U.S. Pat. Nos. 4,450,011, 4,547,224, 4,462,890 to Schilling et al., U.S.Pat. Nos. 4,464,286, 4,561,901, 4,597,799 to Schilling, and U.S. Pat.No. 4,676,927 to Schilling et al. The use of a quaternary amine obtainedby reacting epichlorohydrin, trimethylamine and nonylphenol forsolventless mixes is disclosed in U.S. Pat. No. 3,957,524 to Doughty.

Quick-setting bituminous emulsion compositions wherein amine andalkanolamine salts of alkylbenzenesulfonic acid are used as emulsifiersare disclosed in the U.S. Pat. No. 4,657,595 to Russell.

The general object of this invention is to provide novel versatileanionic emulsifiers for solventless and solvent containing, rapidsetting, mixing grade, oil-in-water bituminous emulsions.

Another object is to provide an anionic bituminous emulsion for mixingwith aggregates whose coating characteristics and set time can bevaried.

SUMMARY OF THE INVENTION

It has been found that emulsifiers capable of producing anionic slurriesmay be obtained by the reaction products of an alkylphenol such asoctylphenol, nonylphenol or dodecylphenol with a polyamine such asaminoethylpiperazine and with an aldehyde such as formaldehyde, followedby a reaction of this product with acrylic acid.

Anionic emulsifiers may also be obtained by using a fatty amidoamine orimidazoline in place of the polyamine. By varying the ratios ofreactants, a series of products with various molecular weights andvarious ratios of hydrophobe/hydrophile can be obtained.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

The anionic slurry seal emulsifier of this invention comprises thereaction product of an alkyl phenol, a polyamine and an aldehyde by theMannich reaction, whereby nitrogen functionality is introduced onto thephenyl ring at the unsubstituted position ortho or para to the phenolichydroxyl group: ##STR1## followed by the reaction of the above productwith acrylic acid through the Michael addition, which gives acarboxyethylated product: ##STR2##

Any alkyl phenol may be used in the practice of this invention, so longas it has at least one unsubstituted position ortho or para to thephenolic hydroxyl group. Preferably the alkyl group has 8-20 carbons,most preferably 8-12 carbons. Examples of suitable alkyl phenols includeoctylphenol, nonylphenol, and dodecylphenol.

Polyamines suitable to undergo the Mannich reaction with formaldehyde orother aldehydes as well as polyaldehydes are imidazoline formingpolyethylene amines and polyamines characterized by at least oneethylene diamine functional group with at least three hydrogens attachedto the two nitrogens. Compounds of this group which are able to giveboth amidoamines and imidazolines are: Ethylene diamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, pentaethylenehexamine, and higher homologues; N-aminoethylpropane diamine,N,N-diaminoethyl substituted butane diamine, pentane diamines and hexanediamines, as well as N-hydroxy ethyl ethylene diamine. These compoundshave the general formulae:

    H.sub.2 NCH.sub.2 CH.sub.2 NHR

    R=H--, CH.sub.3 --, C.sub.2 H.sub.5 --,C.sub.3 H.sub.7 --,

    --CH.sub.2 CH.sub.2 OH, --(CH.sub.2 CH.sub.2 NH).sub.x H

    X=1, 2, 3, 4, . . . 10

or

    R'R"N(CH.sub.2).sub.y NHR'"

    R'=H--, CH.sub.3 --, C.sub.2 H.sub.5 --, C.sub.3 H.sub.7 --, NH.sub.2 CH.sub.2 CH.sub.2 --,

    R"=H--, CH.sub.3 --, C.sub.2 H.sub.5 --,

    R'"=H--, CH.sub.3 --, C.sub.2 H.sub.5 --, C.sub.3 H.sub.7 --, NH.sub.2 CH.sub.2 CH.sub.2 --,

    Y=2, 3, 4, 5, 6.

Amines capable of forming amidoamines but not imidazolines are:1,3-diaminopropane; 1,4-diaminobutane; 1,5-diaminopentane;1,6-diaminohexane; piperazine (1,4-diazocyclohexane); N-aminoethylpiperazine; N-hydroxyethyl piperazine; N-aminopropylpropane diamine;1,3-N-methyl N-aminopropylpropane diamine; 1,3-N,N-dimethylpropanediamine; 1,3-N,N-diethylpropane diamine; 1,3-N,N-dimethylethylenediamine; N-aminohexyl hexane diamine-1,6. Diamines whereby the aminogroups are separated by polyethylene oxide chains or polypropylene oxidechains are also very suited for the Mannich reaction.

These compounds have the general formulae:

    H.sub.2 NCH.sub.2 CH.sub.2 O(CH.sub.2 CH.sub.2 O).sub.x CH.sub.2 CH.sub.2 NH.sub.2

    X=O-100 ##STR3##

    Y=0-100

The above described amines can be further modified by reaction withalkylating agents or cross-linking agents such as are described in U.S.Pat. No. 4,775,744 by P. Schilling et al. in connection with ligninmodification. Modified amines or amine mixtures with increased molecularweight or amines which have additional reactive functionalities such assulfonic acid, carboxyl, hydroxyl, nitrile, and quaternary-ammoniumgroups will be obtained. For the aminomethylation, however, it isnecessary that at least one hydrogen on any of the nitrogens of theparent polyamine be available for the condensation with formaldehyde.

The polyamine as used in the practice of this invention may be a mixtureof two or more of the compounds described above. An example of acommercially available polyamine is the polyamine sold by Union Carbideunder the designation of Amine HH. Amine HH is a blend of polyaminesconsisting mainly of aminoethylpiperazine and triethylene tetramine.

Suitable reactants for the Mannich reaction include the following:aldehydes such as formaldehyde (the preferred reagent), benzaldehyde, orother tertiary aldehydes; dialdehydes such as glutaraldehyde andglyoxal; or unsaturated aldehydes such as acrolein or croton aldehyde.

The emulsifier of the present invention may be prepared by dissolvingthe desired amount of alkylphenol and polyamine in water/isopropanol toyield a 70% solution, adding the required amount of a 37% formaldehydesolution slowly with stirring (the reaction is exothermic) and heatingthe mixture three hours at 90° C. The relative amount of alkylphenol andpolyamine added depends on the hydrophobe/hydrophile ratio desired inthe final product.

The reaction product from the alkyl phenol--polyamine--formaldehydecondensation is blended with acrylic acid and heated to 70° C. for 2-3hours to make the anionic emulsifier.

The use of a polyamine in the Mannich reaction allows for crosslinkingthe polyamine with the aldehyde and results in a series of products withvarious molecular weights and various ratios of hydrophobe/hydrophile.Examples for this type of reaction are the products obtained fromp-dodecylphenol, formaldehyde, and aminoethylpiperazine:

Low molecular weight products: ##STR4##

These formulae represent ideal cases, in reality, the reaction productwill represent mixtures of the products shown above as well as otherisomers.

The above products will be carboxyethylated by the addition of acrylicacid to any primary or secondary nitrogen of the above compounds.

Further products may be obtained by using fatty amidoamines orimidazolines in combination with or in place of the polyamine in thecondensation reaction with an alkyl phenol. Suitable fatty amidoaminesor imidzaolines include the condensation products of polyamines withtall oil fatty acid, or with tall oil fatty acid modified by theaddition of acrylic acid, methacrylic acid, fumaric acid or maleicanhydride. Examples of suitable fatty acid/polyamine condensates arefound in U.S. Pat. No. 4,447,269 issued to Schreuders, et al., and U.S.Pat. No. 4,561,901 issued to Schilling, the disclosures of which areincorporated herein by reference.

Fatty acid/polyamine condensates are available commercially fromWestvaco Corporation and are sold under the trademarks Indulin® RK-1,Indulin® MQK, and Indulin® MQK-1M. In the preparation of an emulsifierwith a fatty acid/polyamine condensate, the fatty acid/polyaminecondensate is blended with alkylphenol and the mixture is diluted withisopropanol. A 37% solution of formaldehyde is added slowly withstirring (the reaction is exothermic) and the mixture is heated at 90°C. for 3 hours.

The reaction product is then blended with acrylic acid and the mixtureis heated to 70° C. for 2-3 hours to obtain the carboxyethylatedproduct.

Condensation products of p-dodecylphenol with formaldehyde and fattyacid/aminoethylpiperazine condensates can be visulized as follows:##STR5##

Acrylic acid adds to primary and secondary nitrogens of the abovecompounds to make the anionic product.

In preparing the anionic bituminous emulsions of this invention, anaqueous basic solution of the emulsifiers described below is intimatelymixed under high shear in a colloid mill. The bitumen content can rangefrom 30% to about 80% by weight, preferably between 60% and 70%. Thedosage of the emulsifier can range from 0.1-10% by weight of theemulsion, preferably between 0.5-2% by weight of the emulsion. Dependenton the emulsifier, a slurry grade anionic emulsion is obtained in a pHrange of from greater than 7 to 12, with the optimum performance at a pHof about 10 to 11.5.

The "bitumen" used in the emulsion may be derived from domestic orforeign crude oil; it also includes bitumen, natural asphalt, petroleumoil, oil residue of paving grade, plastic residue from coal tardistillation, petroleum pitch, and asphalt cements diluted from solvents(cutback asphalts). Practically any viscosity or penetration gradedasphalt cement for use on pavement construction as described in ASTMdesignation D-3381 and D-946 may be emulsified with the aid of theemulsifiers of this invention.

The alkaline soap solutions are normally obtained by suspending thereaction product of alkyl phenol-polyamine-aldehydeacrylic acid or alkylphenol-fatty amidoamine/imidazoline-aldehydeacrylic acid in water towhich a suitable amount of sodium hydroxide or any other suitable baseis added as necessary to obtain the desired pH value of from greaterthan 7 to 12 and a clear emulsifier solution.

Thereafter, the soap solution which is preheated to 55° C. and the fluidasphalt which is preheated to 120°-125° C. are mixed under high shear ina colloid mill to give asphalt emulsions of brown color and creamytexture. Prior to testing according to ASTM D-2444, the emulsions arestored at 70° C. for 16 hours.

The paving slurry seal mixture is prepared by mixing a mineralaggregate, from about 8% to about 20% (based on weight of the aggregate)of the anionic bituminous emulsion, from about 4% to about 16% water andup to 3% of an inorganic additive such as Portland cement, hydratedlime, limestone dust or fly ash, or an organic additive such as polymerlatex. Such additives should comply with the requirements of ASTM D-242.

The aggregates of the invention paving slurry seal mixtures are denselygraded aggregates which range in size from anything passing through aNo. 4 sieve to at least 80% retained on 200 mesh.

The emulsion should be stable during mixing and should set within thedesired time period following application. The setting times can becontrolled with the concentration of emulsifier, the addition of lime,cement or other inorganic additives or an organic additive, which wouldalter the break characteristics of the slurry system. An organicadditive-polymer latex may also be employed to strengthen the matrix.The organic additive is preferably added to the emulsion-aggregateslurry.

In instances where it is desired to alter the performance of theemulsion to obtain improved viscosity at a given asphalt content orimproved stability to dust and fines, blends of the invention anionicemulsifiers with emulsifiers commonly used for anionic bituminousemulsions can be employed. Examples of such emulsifiers are fatty acids,especially tall oil, rosin acids, lignin isolated from sulfite or kraftpulping lignins, and sulfonic acid-containing surfactants such asalkylsulfonates, long chain alkylsulfonates and petroleum sulfonates.

C₁₉ -dicarboxylic acid, C₂₁ -dicarboxylic acid, C₂₂ -tricarboxylic acidor sulfonated fatty acids may also be blended with the inventionemulsifiers prior to the addition of alkali.

Depending on the type of aggregate and its cleanliness, mixing isimproved when aggregate is prewetted with 1-5% water by weight of theaggregate. The performance of the asphalt emulsions in regard to mixingcharacteristics and setting (higher percentage of one-hour washoff coat)can, if necessary, also be improved when, based on the weight ofasphalt, 1-15% of a solvent such a diesel oil is added to the asphaltprior to emulsification. The emulsions prepared with the emulsifiersdisclosed in this invention are stable and can be stored for a longperiod of time until required for use.

Depending on the intended application, the emulsion may be mixed withthe aggregate at a central mixing plant in a large pug mill and the mixtransported to the job site. Alternatively, the emulsion may be taken tothe job site and mixed there, either with a mixing device, such asmotorized mixing equipment, or manually.

As a paving technique at the roadsite, a mobile self-propelled unitcapable of uniformly metering the aggregate, water, inorganic andorganic additives emulsion components, may be used. A typical unit isequipped with separate tanks for aggregate, water, emulsion andadditives which are continually metered into a mixing chamber at apre-determined ratio. The continually fed components are retained in themixing chamber for approximately one minute and then fed into aspreaderbox and applied to the surface to be coated. Batch operatedpneumatic devices can also be used for suitable placement of thebituminous aggregate slurries of this invention.

The practice of this invention may be seen in the following exampleswherein the preparation of various types of slurries of the invention isdescribed.

EXAMPLE 1

The following variety of alkylphenol/polyamine/aldehyde carboxyethylatedemulsifiers were prepared for emulsion-aggregate slurry testing.

Emulsifier A

An emulsifier with a weight ratio of 100:47.5:11.4 of nonylphenol, AmineHH and formaldehyde, respectively, was prepared as follows:

100 g of nonylphenol was blended with 47.5 g Amine HH and the mixturewas diluted with isopropanol to make a 70% solution. 30.8 grams of a 37%solution of formaldehyde was added slowly with stirring and the mixturewas heated to 90° C. for 3 hours.

This product was converted to an anionic emulsifier with a weight ratioof 1:0.33 of the reaction product to acrylic acid as follows:

30 g of the product of the above reaction was blended with 10 g acrylicacid and heated to 70° C. for 2-3 hours.

Emulsifier B

An emulsifier with a weight ratio of 100:94.7:22.8 of nonylphenol, AmineHH and formaldehyde, respectively, was prepared as described above andwas converted to an anionic emulsifier by the addition of acrylic acidin a weight ratio of 1:0.33 of reaction product to acrylic acid,respectively, prepared as described above.

Emulsifier C

100:148:34.2 weight ratio of nonylphenol, Amine HH and formaldehyde,respectively, prepared as above.

1:0.33 weight ratio of reaction product to acrylic acid, respectively,prepared as above.

Emulsifier D

100:71:17.3 weight ratio of dodecylphenol, Amine HH, formaldehyde,respectively, prepared as above.

1:0.33 weight ratio of reaction product to acrylic acid, respectively,prepared as above.

Emulsifier E

100:94.7:22.8 weight ratio of dodecylphenol, Amine HH, formaldehyde,respectively, prepared as above.

1:0.33 weight ratio of reaction product to acrylic acid, respectively,prepared as above.

Emulsifier F

100:148:39.2 weight ratio of dodecylphenol, Amine HH, formaldehyde,respectively, prepared as above.

1:0.33 weight ratio of reaction product to acrylic acid, respectively,prepared as above.

Emulsifier G

Weight ratio of 100:165.7:40 dodecylphenol, Amine HH, formaldehyde,respectively, prepared as above.

1:0.33 weight ratio of reaction product to acrylic acid, respectively,prepared as above.

EXAMPLE 2

Anionic emulsions were prepared with 64% Exxon® 125/150 penetrationasphalt , 1.5% emulsifier at pH 11.5 (adjusted with sodium hydroxide)and water to make up 100% (percentages based on weight of asphalt).Emulsions were prepared for each of the emulsifiers described in Example1.

Next slurries were prepared by mixing 100 grams of Camak (Georgia)granite screenings aggregate, with an anionic aqueous bituminousemulsion, and water in the amounts set out in Table I below. Additionalsamples were prepared with cement or NaOH added to the mix. Thematerials were mixed in a mixing bowl until a homogeneous slurry mixturewas obtained. This mix design is necessary to simulate field conditions.The inability to form a stable slurry within 2 to 3 minutes of mixingtime when proper proportions of each ingredient are used would indicatea mixture in which the materials are not compatible. After the slurrywas mixed, it was spread in a mold placed on an asphalt felt. Theset/break time was measured by blotting the exposed slurry surface witha paper towel. The slurry is considered to be "set" when no stain istransferred to the towel. The cure time could also be measured with acohesion testing device.

The percent of retained asphalt coating on the aggregate was determinedvisually after curing of the mixes at room temperature overnight andboiling in water for 10 minutes.

Many other tests such as described in ASTM D-3910 are used to measurestrength and other physical properties of slurry. The Performance Guidefor Slurry Seal published by the Asphalt Emulsion ManufacturersAssociation can be used to measure the performance of the slurry seal.

The flow behavior, set/break time and percent of retained asphaltcoating on the aggregate were determined for slurries using emulsifiersA, B, C, D, and E with and without Portland cement or NaOH added to themix. Test results are set out in Table I below:

                                      TABLE I                                     __________________________________________________________________________    Anionic Slurry Seal Emulsions Prepared with                                   Carboxyethylated Alkylphenol - Mannich Bases                                           Mixing                                                                        Conditions.sup.(a)                                                                        Flow    Set Time                                                                           %                                           Emulsifier                                                                          pH (%)         Behavior                                                                              (min)                                                                              Coating.sup.(b)                             __________________________________________________________________________    A     11.5     10 W 16 E                                                                           Broke in 05 secs                                                                      --   --                                                   2 C   10 W 16 E                                                                           Broke in 05 secs                                                                      --   --                                                   1 NaOH                                                                              10 W 16 E                                                                           Excellent                                                                             60+  --                                          B     11.5     10 W 16 E                                                                           Broke in 55 secs                                                                      --   --                                                   2 C   10 W 16 E                                                                           Broke in 05 secs                                                                      --   --                                                   0.5 NaOH                                                                            10 W 16 E                                                                           Broke in 05 secs                                                                      --   --                                                   1.0 NaOH                                                                            10 W 16 E                                                                           Broke in 20 secs                                                                      --   --                                                   1.5 NaOH                                                                            10 W 16 E                                                                           Poor    60+  85                                                   2.0 NaOH                                                                            10 W 16 E                                                                           Poor    60+  90                                          C     11.5     10 W 16 E                                                                           Excellent                                                                             60+  90                                                   2 C   10 W 16 E                                                                           Excellent                                                                             15   90                                          D     11.5     10 W 16 E                                                                           Broke in 25 secs                                                                      --   --                                                   2 C   10 W 16 E                                                                           Broke in 05 secs                                                                      --   --                                                   0.5 NaOH                                                                            10 W 16 E                                                                           Excellent                                                                             60+  90                                          E     11.5     10 W 16 E                                                                           Broke in 45 secs                                                                      --   --                                                   2 C   10 W 16 E                                                                           Broke in 05 secs                                                                      --   --                                                   0.5 NaOH                                                                            10 W 16 E                                                                           Excellent                                                                             60+  100                                         F     11.5     10 W 16 E                                                                           Excellent                                                                             60+  85                                                   2 C   10 W 16 E                                                                           Broke in 05 secs                                                                      --   --                                                   0.5 NaOH                                                                            10 W 16 E                                                                           Excellent                                                                             60+  80                                          G     11.5     10 W 16 E                                                                           Excellent                                                                             60+  80                                                   2 C   10 W 16 E                                                                           Broke in 05 secs                                                                      --   --                                                   0.1 NaOH                                                                            10 W 16 E                                                                           Excellent                                                                             60+  90                                          __________________________________________________________________________     .sup.(a) W: water, E: emulsion, C: cement, NaOH: 1% solution in water;        percent based on the weight of the aggregate;                                 .sup.(b) after boiling water for 10 minutes.                             

As Table I shows, the ratio of nonyl or dodecyl phenol to Amine HH hadto be less than 1.0 and the ratio of phenol to formaldehyde had to beless than 3 to produce emulsions which could be mixed with aggregate for60 seconds without the addition of a mixing aid. Addition of 0.5-1.5parts 1% NaOH solution per 100 parts of aggregate resulted in fluidslurry seal mixes independent of the composition of emulsifier. In thepresence of 2 parts cement the emulsions broke prematurely (except C).The retained coating of the aggregate after boiling in water for 10minutes was good.

EXAMPLE 3

The following variety of carboxyethylated alkylphenol--fattyamine--aldehyde emulsifiers were prepared for emulsion--aggregate slurrytesting:

Emulsifier H

An emulsifier with a weight ratio of 100:10:0.74 of Indulin MQK,nonylphenol and formaldehyde, respectively was prepared as follows:

100 g of Indulin MQK was blended with 10 g nonylphenol and the mixturewas diluted with isopropanol, 2 g of a 37% formaldehyde solution wasadded with good stirring, and the mixture was heated to 90° C. for 3hours.

This reaction product was converted to an anionic emulsifier with aweight ratio of 1:0.33 of the reaction product to acrylic acid asfollows:

30 g of the reaction product was blended with 10 g acrylic acid and themixture was heated to 70° C. for 2-3 hours.

Emulsifier I

An emulsifier with a weight ratio of 100:20:1.48 of Indulin MQK,nonylphenol and formaldehyde, respectively, was prepared as above andwas converted to an anionic emulsifier by the addition of acrylic acidin a weight ratio of 1:0.33 of the reaction product to acrylic acid,respectively, prepared as described above.

Emulsifier J

Weight ratio of 100:30:2.22 of Indulin MQK, nonylphenol, andformaldehyde, respectively, prepared as above.

1:0.33 weight ratio of reaction product to acrylic acid, respectively,prepared as above.

Emulsifier K

Weight ratio of 100:25:1.85 of Indulin MQK-1M, nonylphenol andformaldehyde, respectively, prepared as above.

1:0.33 weight ratio of reaction product to acrylic acid, respectively,prepared as above.

Emulsifier L

Weight ratio of 100:50:3.7 of Indulin MQK-1M, nonylphenol andformaldehyde, respectively, prepared as above.

1:0.33 weight ratio of reaction product to acrylic acid, respectively,prepared as above.

EXAMPLE 4

Slurries were prepared and tested as described in Example 2, above.Results of testing are set out in Table II, below.

                                      TABLE II                                    __________________________________________________________________________    Anionic Slurry Seal Emulsions Prepared with                                   Carboxyethylated Indulin MQK Nonylphenol-Formaldehyde and                     Indulin MQK-1M Nonylphenol-Formaldehyde Condensates                                    Mixing                                                                        Conditions.sup.(a)                                                                      Flow     Set Time                                                                           %                                            Emulsifier                                                                          pH %         Behavior (min)                                                                              Coating.sup.(b)                              __________________________________________________________________________    H     11.5  10 W 16 E                                                                            Excellent                                                                              60+  75                                                    2 C                                                                              10 W 16 E                                                                            Excellent                                                                              15   75                                           I     11.5  10 W 16 E                                                                            Excellent                                                                              60+  95                                                    2 C                                                                              10 W 16 E                                                                            Good     10   80                                           J     11.5  10 W 16 E                                                                            Excellent                                                                              60+  90                                                    2 C                                                                              10 W 16 E                                                                            Good     10   80                                           K     11.5  10 W 16 E                                                                            Excellent                                                                              60+  75                                                    2 C                                                                              10 W 16 E                                                                            Broke in 20 secs.                                                                      --   --                                           L     11.5  10 W 16 E                                                                            Excellent                                                                              60+  90                                                    2 C                                                                              10 W 16 E                                                                            Broke in 10 secs.                                                                      --   --                                           __________________________________________________________________________     .sup.(a) W: water, E: emulsion, C: cement, percent based on the weight of     the aggregate;                                                                .sup.(b) after boiling water for 10 minutes.                             

As Table II shows, emulsions prepared with modified INDULIN MQK could bemixed with aggregate with and without 2% cement present in the mix.Emulsions prepared with modified INDULIN MQK-1M could be mixed for 60seconds without the addition of cement, but broke prematurely whencement was present. The retained coating after subjecting the cured mixto the 10 minute boiling test was good.

While the invention has been described and illustrated herein byreferences to various specific materials, procedures and examples, it isunderstood that the invention is not restricted to the particularmaterials, combinations of materials, and procedures selected for thatpurpose. Numerous variations of such details can be employed, as will beappreciated by those skilled in the art.

I claim:
 1. A composition of matter comprising the reaction product of (1) acrylic acid reacted with (2) the reaction product of (a) an alkyl phenol of the general form (b) an aldehyde, and (c) a polyamine.
 2. The composition of claim 1, wherein said alkyl group comprises from 8 to 20 carbons.
 3. The composition of claim 1 wherein said alkyl phenol is selected from the group of octylphenol, nonylphenol and dodecylphenol.
 4. The composition of claim 1 wherein said aldehyde is formaldehyde.
 5. The composition of claim 1 wherein said polyamine is a blend of polyamines comprising aminoethylpiperazine and triethylene tetramine.
 6. The composition of claim 1 wherein said alkyl phenol is selected from the group of octylphenol, nonylphenol and dodecylphenol, said aldehyde is formaldehyde, and said polyamine is a blend of polyamines comprising aminoethylpiperazine and triethylene tetramine.
 7. A composition of matter comprising the reaction product of (1) acrylic acid reacted with (2) the reaction product of (a) an alkyl phenol of the general form ##STR6## where R represents a linear or branched alkyl group, (b) an aldehyde, and (c) the reaction product of a polyamine and a compound selected from the group of a tall oil fatty acid, a polycarboxylic acid corresponding to the formula ##STR7## and a polycarboxylic acid corresponding to the formula ##STR8## wherein x and y are integers from 3 to 9, x and y together equal 12, at least one Z is a carboxylic acid group and any remaining Z is hydrogen.
 8. The composition of claim 7 wherein said alkyl group comprises from 8 to 20 carbons.
 9. The composition of claim 7 wherein said alkyl phenol is selected from the group of octylphenol, nonylphenol and dodecylphenol.
 10. The composition of claim 7 wherein said aldehyde is formaldehyde.
 11. The composition of claim 7 wherein said polyamine is a blend of polyamines comprising aminoethylpiperazine and triethylene tetramine.
 12. The composition of claim 7 wherein said alkyl phenol is selected from the group of octylphenol, nonylphenol and dodecylphenol, said aldehyde is formaldehyde, and said polyamine is a blend of polyamines comprising aminoethylpiperazine and triethylene tetramine. 